S. K. Ghosh, R. Singh, G. C. Singh
FULL PAPER
1 H), 6.99 (s, 1 H), 7.02 (d, J ϭ 8.2 Hz, 1 H) ppm. 13C NMR
7 Hz, 6 H), 2.16 (s, 3 H), 3.47 (s, 2 H), 4.04 (q, J ϭ 7 Hz, 4 H),
(50 MHz, CDCl3): δ ϭ 13.92 (2 C), 20.35, 20.95, 55.06, 59.41, 61.35 5.40 (s, 1 H), 5.44 (s, 1 H), 7.18Ϫ7.26 (m, 8 H), 7.42 (d, J ϭ 8.4 Hz,
(2 C), 109.86, 120.53, 129.12 (2 C), 129.61, 131.67, 145.12, 154.28,
2 H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 13.63 (2 C), 24.39,
171.66 (2 C) ppm. EI MS: m/z (%) ϭ 321 (3) [M ϩ 1]ϩ, 320 (15) 41.80, 61.40 (2 C), 64.55, 119.07 (2 C), 120.21, 126.83, 127.81 (2
[M]ϩ, 247 (100), 229 (9), 219 (50), 201 (17), 189 (14), 173 (31), 159
C), 128.33 (2 C), 130.38 (2 C), 136.32, 137.12, 137.40, 145.28,
(16), 158 (17), 128 (9), 115 (12). C18H24O5 (320.4): calcd. C 67.48, 168.64, 169.76 (2 C) ppm. ESI MS: m/z (%) ϭ 433 (27) [M ϩ 24]ϩ,
H 7.5; found C 67.32, H 7.75.
432 (100) [M ϩ 24]ϩ, 410 (5) [M ϩ 1]ϩ. C24H27NO5 (409.5): calcd.
C 70.40, H 6.65, N 3.42; found C 70.35, H 6.75, N 3.40.
Ethyl 2-Ethoxycarbonyl-2-methyl-3-(1-naphthyl)-3-butenoate (5d):
Compound 5d was obtained in 77% yield from the reaction be-
tween 3a ϩ 4a and 1-iodonaphthalene under the indicated con-
ditions after purification by column chromatography. Rf ϭ 0.3
Ethyl 2-Ethoxycarbonyl-2-methyl-3-(4-trifluoromethylphenyl)-3-but-
enoate (5h): Compound 5h was obtained in 84% yield from the
reaction between 3a ϩ 4a and 1-iodo-4-trifluoromethylbenzene un-
der the indicated conditions after purification by column chroma-
tography. Rf ϭ 0.29 (hexane/EtOAc, 95:5). IR (neat): ν˜ ϭ 3099,
(hexane/EtOAc, 96:4). IR (neat): ν˜ ϭ 3089, 1732, 1634, 863 cmϪ1
.
1H NMR (200 MHz, CDCl3): δ ϭ 1.12Ϫ1.34 (m, 6 H), 1.50 (s, 3
H), 4.00Ϫ4.32 (m, 4 H), 5.43 (s, 1 H), 5.80 (s, 1 H), 7.37Ϫ7.49 (m,
4 H), 7.75Ϫ7.85 (m, 2 H), 8.01Ϫ8.09 (m, 1 H) ppm. 13C NMR
(50 MHz, CDCl3): δ ϭ 13.70 (2 C), 21.60, 60.40, 61.52 (2 C),
121.55, 124.81, 125.54, 125.73, 125.79, 126.26, 127.53, 127.92,
132.56, 133.42, 138.30, 144.04, 171.25 (2 C) ppm. EI MS: m/z
(%) ϭ 327 (9) [M ϩ 1]ϩ, 326 (29) [M]ϩ, 253 (31), 252 (61), 225
(29), 223 (13), 207 (28), 206 (32), 179 (100), 178 (32), 165 (44), 153
(28), 152 (29), 128 (14). C20H22O4 (326.4): calcd. C 73.60, H 6.79;
found C 73.35, H 7.10.
1732, 1615, 1327, 854 cmϪ1 1H NMR (200 MHz, CDCl3): δ ϭ
.
1.19 (t, J ϭ 7.1 Hz, 6 H), 1.62 (s, 3 H), 4.17 (q, J ϭ 7.1 Hz, 4 H),
5.38 (s, 1 H), 5.44 (s, 1 H), 7.40 (d, J ϭ 8.1 Hz, 2 H), 7.54 (d, J ϭ
8.1 Hz, 2 H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 13.75 (2 C),
22.19, 59.77, 61.74 (2 C), 119.35, 124.08 (q, J ϭ 270 Hz), 124.76 (2
C), 128.68 (2 C), 129.47 (q, J ϭ 32.1 Hz), 144.57, 146.74, 170.96
(2 C) ppm. EI MS: m/z (%) ϭ 345 (0.03) [M ϩ 1]ϩ, 344 (0.03)
[M]ϩ, 325 (3), 299 (1), 271 (77), 243 (100), 225 (10), 197 (24), 177
(16), 159 (17), 129 (21), 128 (25). C17H19F3O4 (344.3): calcd. C
59.30, H 5.56; found C 59.06, H 5.78.
Ethyl 3-(4-Acetamidophenyl)-2-ethoxycarbonyl-2-methyl-3-buteno-
ate (5e): Compound 5e was obtained in 92% yield from the reaction
between 3a ϩ 4a and 4-acetamidoiodobenzene under the indicated
conditions after purification by column chromatography. Rf ϭ 0.28
(hexane/EtOAc, 55:45). IR (neat): ν˜ ϭ 3366, 3306, 3184, 3108,
3047, 1729, 1695, 1673, 1596, 1527, 848 cmϪ1. 1H NMR (200 MHz,
CDCl3): δ ϭ 1.22 (t, J ϭ 7.2 Hz, 6 H), 1.59 (s, 3 H), 2.17 (s, 3 H),
4.18 (q, J ϭ 7.2 Hz, 4 H), 5.31 (s, 1 H), 5.33 (s, 1 H), 7.22 (d, J ϭ
8.4 Hz, 2 H), 7.30 (s, broad, 1 H), 7.42 (d, J ϭ 8.4 Hz, 2 H) ppm.
13C NMR (50 MHz, CDCl3): δ ϭ 13.80 (2 C), 22.13, 24.40, 59.99,
61.66 (2 C), 117.83, 119.11 (2 C), 128.73 (2 C), 136.36, 137.33,
147.04, 168.67, 171.36 (2 C) ppm. EI MS: m/z (%) ϭ 334 (0.6) [M
ϩ 1]ϩ, 333 (3) [M]ϩ, 260 (100), 232 (92), 214 (9), 186 (12), 162 (10),
144 (69), 130 (31), 118 (26), 106 (17), 77 (8), 43 (44). C18H23NO5
(333.4): calcd. C 64.85, H 6.95, N 4.20; found C 64.62, H 7.17,
N 4.26.
Supporting Information: 1H and 13C NMR spectra of 3a and 3b;
4a and 4b; 5aϪ5h; 6a and 7a (29 pages) (see also the footnote on
the first page of this article.
Acknowledgments
We are grateful to Prof. Scott E. Denmark for helpful suggestions.
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Ethyl 2-Benzyl-2-ethoxycarbonyl-3-(4-methoxyphenyl)-3-butenoate
(5f): Compound 5f was obtained in 75% yield from the reaction
between 3b ϩ 4b and 4-iodoanisole under the indicated conditions
after purification by column chromatography. Rf ϭ 0.37(hexane/
EtOAc, 92:8). IR (neat): ν˜ ϭ 3087, 1736, 1608, 837 cmϪ1. 1H NMR
(200 MHz, CDCl3): δ ϭ 1.08 (t, J ϭ 7.2 Hz, 6 H), 3.46 (s, 2 H),
3.79 (s, 3 H), 4.04 (q, J ϭ 7.2 Hz, 4 H), 5.37 (s, 1 H), 5.40 (s, 1 H),
6.81 (d, J ϭ 8.6 Hz, 2 H), 7.19 (br. s, 5 H), 7.20 (d, J ϭ 8.6 Hz, 2
H) ppm. 13C NMR (50 MHz, CDCl3): δ ϭ 13.68 (2 C), 41.73,
55.20, 61.34 (2 C), 64.77, 113.21 (2 C), 120.05, 126.75, 127.77 (2 C),
129.10 (2 C), 130.54 (2 C), 133.93, 136.57, 145.23, 158.84, 169.87 (2
C) ppm. EI MS: m/z (%) ϭ 383 (0.4) [M ϩ 1]ϩ, 382 (1) [M]ϩ, 336
(1.5), 333 (2.5), 299 (2.5), 292 (3.5), 309 (2.5), 291 (19), 245 (5.5),
235 (11), 218 (9.5), 217 (100), 189 (12), 161 (6), 149 (14), 145 (26),
135 (27), 121 (20), 91 (51). C23H26O5 (382.5): calcd. C 72.23, H
6.85; found C 72.24, H 7.21.
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Ethyl 3-(4-Acetamidophenyl)-2-benzyl-2-ethoxycarbonyl-3-buteno-
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tion between 3b ϩ 4b and 4-acetamidoiodobenzene under the indi-
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M.p. 104Ϫ105 °C; Rf ϭ 0.32 (hexane/EtOAc, 6:4). IR (CHCl3):
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1522, 837 cmϪ1
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1H NMR (200 MHz, CDCl3): δ ϭ 1.08 (t, J ϭ
1994, 465, 97Ϫ100.
4146
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2004, 4141Ϫ4147